US10457775B2 - Method for producing high molecular weight polyoxyalkylene polyols - Google Patents

Method for producing high molecular weight polyoxyalkylene polyols Download PDF

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US10457775B2
US10457775B2 US15/754,491 US201615754491A US10457775B2 US 10457775 B2 US10457775 B2 US 10457775B2 US 201615754491 A US201615754491 A US 201615754491A US 10457775 B2 US10457775 B2 US 10457775B2
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alkylene oxide
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Klaus Lorenz
Christian Steinlein
Horst Zwick
Markus Bodenmüller
Stephan Eckelmann
Friedhelm Baer
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Covestro Deutschland AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
    • C08G2650/24—Polymeric initiators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics

Definitions

  • the present invention provides an improved process for preparing polyoxyalkylene polyols having calculated equivalent molar masses of 9500 to 23 000 g/mol, preferably of 9500 to 20 000 g/mol, more preferably of 9700 to 16 000 g/mol.
  • Polyoxyalkylene polyols suitable for the preparation of polyurethanes can be obtained via various preparation processes.
  • One process of significance on the industrial scale is the base-catalyzed addition of alkylene oxides onto H-functional starter compounds, and another is the use of double metal cyanide compounds as catalysts (“DMC catalysts”) for the addition of alkylene oxides onto H-functional starter compounds.
  • DMC catalysts double metal cyanide compounds as catalysts
  • the (Lewis) acid-catalyzed addition of alkylene oxides onto suitable starter compounds is of minor importance.
  • DMC catalysts has made it possible to advance the addition of alkylene oxides, especially propylene oxide, onto H-functional starter compounds down to very low OH numbers, i.e. high equivalent molar masses, without any significant degree of occurrence of the abovementioned isomerization of propylene oxide to allyl alcohol.
  • Highly active DMC catalysts which are described, for example, in U.S. Pat. No.
  • EP-A 700949, EP-A 743093, EP-A 761708, WO-A 97/40086, WO-A 98/16310 and WO-A 00/47649 additionally have exceptionally high activity and enable polyoxyalkylene polyol preparation at very low catalyst concentrations (100 ppm or less), such that removal of the catalyst from the finished product is no longer required.
  • a typical example is that of the highly active DMC catalysts which are described in EP-A 700949 and contain not only a double metal cyanide compound (e.g. zinc hexacyanocobaltate(III)) and an organic complex ligand (e.g. tert-butanol) but also a polyoxyalkylene compound having a number-average molecular weight greater than 500 g/mol.
  • the equivalent molar mass of materials containing active hydrogen atoms is understood to mean the total mass of the material containing active hydrogen atoms divided by the number of active hydrogen atoms.
  • materials containing hydroxyl groups for example polyoxyalkylene polyols
  • they are related to the OH number (hydroxyl number) as follows: equivalent molar mass 56100/(OH number [mg KOH/g]) (I)
  • the equivalent molar mass of the polyoxyalkylene polyols is thus ascertained according to formula (I), where the hydroxyl number of the polyoxyalkylene polyol is determined according to DIN 53240.
  • the calculated equivalent molar mass is determined by inserting the calculated OH number into formula (I).
  • DMC-catalyzed preparation of alkylene oxide addition products having high equivalent molar masses and the use thereof for preparation of polyurethane- or polyurea-based materials are known to those skilled in the art.
  • DE-A 4117679 and U.S. Pat. No. 5,096,993 disclose the use of polyhydroxy or polyamine compounds having molar masses of up to 30 000 Da for preparation of soft polyurethane or polyurea elastomers by the reactive injection molding process (“RIM” methodology).
  • WO-A 9104997 discloses polyoxyalkylenetriols having molar masses of up to 30000 Da as polyoxyalkylene component of isocyanate-terminated prepolymers which are used in high-quality polyurethane sealant systems.
  • EP-A 1316573 discloses a process for obtaining rapidly demoldable flexible foam bodies having good sustained use properties, the production of which involves using polyoxyalkylene polyols having equivalent molar masses of preferably 5000 to 11 000 Da that have been prepared by DMC catalysis as polyol component.
  • EP-A 0425694 discloses isocyanate-terminated polyoxyalkylene prepolymers, the polyoxyalkylene component of which has equivalent molar masses of up to 15 000 Da.
  • Polyoxyalkylene polyols of this kind are obtained via DMC catalysis.
  • Polyoxyalkylenes prepared via DMC catalysis and having equivalent molar masses of up to 15 000 Da are used in EP-A 0723561 as starting compounds for production of moisture-curing sealant systems based on polymers containing silane groups.
  • WO-A 2013/000915 proposes solving this problem by metering the alkylene oxides into the reactor within 15 to 23 h. If the alkylene oxides are supplied to the reactor within this metering time window, it is indeed possible to obtain polyoxyalkylene polyols of relatively low viscosity with high calculated equivalent molar masses.
  • a distinct disadvantage of this process is the long run time of the individual polymerization batches which limits the plant capacity (space-time yield).
  • the object is surprisingly achieved by a process for preparing a polyoxyalkylene polyol by reacting at least one H-functional starter compound with at least one alkylene oxide in the presence of a double metal cyanide catalyst in a reactor, by supplying the reactor continuously or discontinuously with the at least one alkylene oxide from a time t 1 until a time t 3 , and by already commencing supply of the reactor with a portion of the total amount of the at least one alkylene oxide to be fed in for preparation of the desired polyoxyalkylene polyol from an earlier time t 0 ⁇ t 1 ,
  • r AO n AO n OH ⁇ ⁇ ⁇ ⁇ t ⁇ OH ⁇ ⁇ N target / ( mg KOH ⁇ g - 1 )
  • FIG. 1 illustrates the alkylene oxide metering rate profiles ⁇ dot over (n) ⁇ (AO), shown as a function of the metering time.
  • FIG. 2 illustrates the cumulated amounts of alkylene oxide metered in n(AO), shown as a function of the metering time.
  • the polyoxyalkylene polyols obtainable by the process of the invention after the total alkylene oxide metering time has elapsed, have a calculated equivalent molar mass of 9500 g ⁇ mol ⁇ 1 to 23 000 g ⁇ mol ⁇ 1 , preferably of 9550 g ⁇ mol ⁇ 1 to 23 000 g ⁇ mol ⁇ 1 , more preferably of 9550 g ⁇ mol ⁇ 1 to 20 000 g ⁇ mol ⁇ 1 and most preferably of 9700 to 16 000 g/mol.
  • the alkylene oxide(s) can in principle be metered in as fast as desired, meaning that the alkylene oxide metering rate is subject solely to the limitation of provision of sufficient cooling performance.
  • WO-A 2013/000915 does admittedly point out that the alkylene oxide metering rates can be altered and preferably lowered during the batch run time.
  • WO-A 2013/000915 does not give any hints that only after surpassing a calculated equivalent molar mass of at least 8000 g/mol does it become absolutely necessary to lower the metering rate in order to obtain high molecular weight polyols having low viscosities, which constitutes a prerequisite for the attainment of short batch run times and hence for the achievement of an important aim of the invention.
  • the DMC catalyst in a process step preceding the polymerization, can at first be separately activated by already commencing supply of a portion of the total amount of the at least one alkylene oxide to be fed in for preparation of the desired polyoxyalkylene polyol from an earlier time t 0 until not later than a time t 1 .
  • the DMC catalyst normally up to 20% by mass of alkylene oxide, preferably 2% up to 20% by mass of alkylene oxide, is used, based on the amount of the at least one H-functional starter compound used.
  • the addition of the at least one alkylene oxide can take place before, during or after the heating of the reactor contents to reaction temperature; it preferably follows attainment of the reaction temperature.
  • the metered addition of the amount of alkylene oxide needed for the activation of the DMC catalyst commences at time t 0 .
  • the metered addition of alkylene oxide has been stopped once typically 2% to 20% by mass of alkylene oxide, based on the mass of the at least one H-functional starter compound used, have been metered in
  • the activation of the double metal cyanide catalyst is manifested by an accelerated drop in the reactor pressure, which indicates the commencement of alkylene oxide conversion.
  • the remaining amount of alkylene oxide or alkylene oxide mixture is fed into the reaction mixture.
  • H-functional starter compounds are those compounds containing at least one Zerewitinoff-active hydrogen atom, sometimes also referred to merely as “active hydrogen”.
  • a hydrogen bonded to C, N, O or S is referred to as Zerewitinoff-active hydrogen when it affords methane by reaction with methylmagnesium iodide, by a method discovered by Zerewitinoff.
  • Typical examples of compounds having Zerewitinoff-active hydrogen are compounds containing carboxyl, hydroxyl or thiol groups as functional groups. The functionality is understood to mean the number of Zerewitinoff-active hydrogen atoms per molecule of the H-functional starter compounds.
  • the at least one H-functional starter compound here usually has functionalities of 1 to 35, preferably of 2 to 8, more preferably 2 to 3, most preferably of 2.
  • the molar masses of suitable H-functional starter compounds are generally from 18 g/mol to 1200 g/mol. If a mixture of H-functional starter compounds is used, the functionality of this mixture is the number-average functionality of the H-functional starter compounds.
  • Suitable starter compounds are methanol, ethanol, 1-propanol, 2-propanol and higher aliphatic monools, especially fatty alcohols, phenol, alkyl-substituted phenols, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, hexanediol, pentanediol, 3-methylpentane-1,5-diol, dodecane-1,12-diol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, hydroquinone, catechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, and methylol-containing condensates of formaldehyde and phenol or urea.
  • Examples are ring-opening products of phthalic anhydride, succinic anhydride and maleic anhydride on the one hand, and ethylene glycol, diethylene glycol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, hexanediol, pentanediol, 3-methylpentane-1,5-diol, dodecane-1,12-diol, glycerol, trimethylolpropane, pentaerythritol or sorbitol on the other hand.
  • mono- or polyfunctional carboxylic acids directly as starter compounds.
  • alkylene oxide addition products of the H-functional starter compounds mentioned i.e. polyoxyalkylene polyols preferably having OH numbers of 16 to 1000 mg KOH/g, more preferably 40 to 1000 mg KOH/g, as exclusive starters for the process of the invention, or to add them to the abovementioned starters.
  • These alkylene oxide addition products usable as (co-)starters can in turn be prepared via DMC catalysis or base catalysis.
  • Polyester polyols suitable for this purpose can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms and polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, by known processes.
  • H-functional starter substances used as (co-)starters may be polycarbonate polyols, polyester carbonate polyols or polyoxyalkylene carbonate polyols, preferably polycarbonate diols, polyester carbonate diols or polyoxyalkylene carbonate diols, preferably each having OH numbers in the range from 20 to 800 mg KOH/g. These are prepared, for example, by reaction of phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate with difunctional or higher-functionality alcohols or polyester polyols or polyoxyalkylene polyols.
  • H-functional starter compounds having hydroxyl groups for example methanol, ethanol, 1-propanol, 2-propanol and higher aliphatic monools, especially fatty alcohols, phenol, alkyl-substituted phenols, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, hexanediol, pentanediol, 3-methylpentane-1,5-diol, dodecane-1,12-diol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, hydroquinone, catechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, methylol-containing condensates
  • DMC catalysts suitable for the process of the invention are known in principle from the prior art (see, for example, U.S. Pat. Nos. 3,404,109, 3,829,505, 3,941,849 and 5,158,922).
  • DMC catalysts which are described, for example, in U.S. Pat. No. 5,470,813, EP-A 700949, EP-A 743093, EP-A 761708, WO 97/40086, WO 98/16310 and WO 00/47649, have a very high activity in the polymerization of alkylene oxides and enable the preparation of polyoxyalkylene polyols under optimal conditions at very low catalyst concentrations (100 ppm or less), such that removal of the catalyst from the finished product is generally no longer required.
  • a typical example is that of the highly active DMC catalysts which are described in EP-A 700949 and contain not only a double metal cyanide compound (e.g. zinc hexacyanocobaltate(III)) and an organic complex ligand (e.g. tert-butanol) but also a polyoxyalkylene compound having a number-average molecular weight greater than 500 g/mol. It is also possible to use the alkaline DMC catalysts disclosed in EP application number 10163170.3.
  • Cyanide-free metal salts suitable for preparation of the double metal cyanide compounds preferably have the general formula (II) M(X) n (II) where M is selected from the metal cations Zn 2+ , Fe 2+ , Ni 2+ , Mn 2+ , Co 2+ , Sr 2+ , Sn 2+ , Pb 2+ and Cu 2+ ; M is preferably Zn 2+ , Fe 2+ , Co 2+ or Ni 2+ , X are one or more (i.e. different) anions, preferably an anion selected from the group of the halides (i.e.
  • halides i.e. fluoride, chloride, bromide, iodide
  • hydroxide sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate or nitrate
  • sulfate carbonate
  • cyanate thiocyanate
  • isocyanate isothi
  • cyanide-free metal salts examples include zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, iron(II) chloride, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) chloride and nickel(II) nitrate. It is also possible to use mixtures of different metal salts.
  • Metal cyanide salts suitable for preparation of the double metal cyanide compounds preferably have the general formula (VI) (Y) a M′(CN) b (A) c (VI) where M′ is selected from one or more metal cations from the group consisting of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V); M′ is preferably one or more metal cations from the group consisting of Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II), Y is selected from one or more metal cations from the group consisting of alkali metal (i.e.
  • A is selected from one or more anions from the group consisting of halides (i.e.
  • a, b and c are integers, the values for a, b and c being selected so as to assure electronic neutrality of the metal cyanide salt; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0.
  • Suitable metal cyanide salts are potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III) and lithium hexacyanocobaltate(III).
  • Preferred double metal cyanide compounds present in the inventive DMC catalysts are compounds of the general formula (VII) M x [M′ x ,(CN) y ] z (VII) in which M is defined as in formulae (II) to (V) and M′ is as defined in formula (VI), and x, x′, y and z are integers and are chosen so as to give an electronically neutral double metal cyanide compound.
  • M Zn(II), Fe(II), Co(II) or Ni(II) and
  • M′ Co(III), Fe(III), Cr(III) or Ir(III).
  • Suitable double metal cyanide compounds are zinc hexacyanocobaltate(III), zinc hexacyanoiridate(III), zinc hexacyanoferrate(III) and cobalt(II) hexacyanocobaltate(III). Further examples of suitable double metal cyanide compounds can be found, for example, in U.S. Pat. No. 5,158,922 (column 8, lines 29-66). Particular preference is given to using zinc hexacyanocobaltate (III).
  • organic complex ligands added in the preparation of the DMC catalysts are disclosed, for example, in U.S. Pat. No. 5,158,922 (see especially column 6 lines 9 to 65), U.S. Pat. Nos. 3,404,109, 3,829,505, 3,941,849, EP-A 700949, EP-A 761708, JP-A 4145123, U.S. Pat. No. 5,470,813, EP-A 743 093 and WO-A 97/40086.
  • organic complex ligands used are water-soluble organic compounds having heteroatoms such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the double metal cyanide compound.
  • Preferred organic complex ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof.
  • Particularly preferred organic complex ligands are aliphatic ethers (such as dimethoxyethane), water-soluble aliphatic alcohols (such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), compounds containing both aliphatic or cycloaliphatic ether groups and aliphatic hydroxyl groups (for example ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol monomethyl ether and 3-methyl-3-oxetanemethanol).
  • aliphatic ethers such as dim
  • Most preferred organic complex ligands are selected from one or more compounds from the group consisting of dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetanemethanol.
  • the aqueous solutions of the metal salt e.g. zinc chloride
  • metal cyanide salt i.e. at least a molar ratio of cyanide-free metal salt to metal cyanide salt of 2.25:1.00
  • the metal cyanide salt e.g. potassium hexacyanocobaltate
  • the organic complex ligand e.g. tert-butanol
  • the organic complex ligand may be present in the aqueous solution of the cyanide-free metal salt and/or of the metal cyanide salt, or it is added directly to the suspension obtained after precipitation of the double metal cyanide compound. It has been found to be advantageous to mix the aqueous solutions of the cyanide-free metal salt and of the metal cyanide salt and the organic complex ligands by stirring vigorously.
  • the suspension formed in the first step is subsequently treated with a further complex-forming component.
  • the complex-forming component is preferably used in a mixture with water and organic complex ligand.
  • a preferred process for performing the first step i.e. the preparation of the suspension
  • the solids i.e. the precursor of the catalyst of the invention
  • the solids are isolated from the suspension by known techniques, such as centrifugation or filtration.
  • the isolated solid is subsequently washed in a third process step with an aqueous solution of the organic complex ligand (for example by resuspension and subsequent reisolation by filtration or centrifugation).
  • an aqueous solution of the organic complex ligand for example by resuspension and subsequent reisolation by filtration or centrifugation.
  • the amount of the organic complex ligand in the aqueous wash solution is between 40% and 80% by mass, based on the overall solution.
  • the aqueous wash solution is admixed with one or more further complex-forming component(s), preferably in the range between 0.5% and 5% by mass, based on the overall solution.
  • the isolated solid it is also advantageous to wash the isolated solid more than once.
  • the first washing procedure can be repeated.
  • non-aqueous solutions for further washing operations for example a mixture of organic complex ligand and further complex-forming component.
  • the isolated and optionally washed solid is subsequently dried at temperatures of generally 20-100° C. and at absolute pressures of generally 0.1 mbar to atmospheric pressure (1013 mbar), optionally after pulverizing.
  • the double metal cyanide catalyst is used in proportions by mass of 10 ppm to 1000 ppm, preferably in proportions by mass of 15 to 500 ppm, more preferably in proportions by mass of 20 to 300 ppm and most preferably in proportions by mass of 25 to 150 ppm, based in each case on the total mass of the reaction mixture in the reactor at time t 3 .
  • the DMC catalyst remains in the end product, but it can also be removed, for example by treatment with adsorbents.
  • Processes for removing DMC catalysts are described, for example, in U.S. Pat. No. 4,987,271, DE-A 3132258, EP-A 406440, U.S. Pat. Nos. 5,391,722, 5,099,075, 4,721,818, 4,877,906 and EP-A 385619.
  • the at least one alkylene oxide has 2 to 24 carbon atoms.
  • the alkylene oxides having 2 to 24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-1,2-pentene oxide, butadiene monoxide, isoprene monoxide, is
  • the alkylene oxide used is preferably ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide. If mixtures of ethylene oxide and propylene oxide are used, these preferably have up to 75% by mass of ethylene oxide, more preferably up to 50% by mass of ethylene oxide and most preferably up to 30% by mass of ethylene oxide, based on the total mass of the mixture of ethylene oxide and propylene oxide. Particular preference is given to using exclusively propylene oxide.
  • the alkylene oxides can be supplied to the reactor as individual components or as a mixture. It is likewise possible to feed two or more alkylene oxides to the reactor in succession, by which means it is possible to implement polyoxyalkylene chains with block structure. In the metered addition of two or more alkylene oxides, it is possible to change the composition of the alkylene oxide stream supplied continuously or instantaneously.
  • Further monomers copolymerizable with alkylene oxides under DMC catalysis by the process of the invention are, for example, aliphatic lactones, aromatic lactones, lactides, cyclic carbonates having preferably at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group, aliphatic cyclic anhydrides and aromatic cyclic anhydrides and carbon dioxide.
  • Aliphatic or aromatic lactones are cyclic compounds containing an ester bond in the ring.
  • Preferred compounds are 4-membered-ring lactones such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -isovalerolactone, ⁇ -caprolactone, ⁇ -isocaprolactone, ⁇ -methyl- ⁇ -valerolactone, 5-membered-ring lactones, such as ⁇ -butyrolactone, ⁇ -valerolactone, 5-methylfuran-2(3H)-one, 5-methylidenedihydrofuran-2(3H)-one, 5-hydroxyfuran-2(5H)-one, 2-benzofuran-1(3H)-one and 6-methyl-2-benzofuran-1(3H)-one, 6-membered-ring lactones, such as ⁇ -valerolactone, 1,4-dioxan-2-one, dihydrocoumarin, 1H-isochromen-1-one, 8H-pyr
  • Lactides are cyclic compounds containing two or more ester bonds in the ring.
  • Preferred compounds are glycolide (1,4-dioxane-2,5-dione), L-lactide (L-3,6-dimethyl-1,4-dioxane-2,5-dione), D-lactide, DL-lactide, mesolactide and 3-methyl-1,4-dioxane-2,5-dione, 3-hexyl-6-methyl-1,4-dioxane-2,5-dione, and 3,6-di(but-3-en-1-yl)-1,4-dioxane-2,5-dione (in each case inclusive of optically active forms). Particular preference is given to L-lactide.
  • Cyclic carbonates used are preferably compounds having at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group.
  • Preferred compounds are trimethylene carbonate, neopentyl glycol carbonate (5,5-dimethyl-1,3-dioxan-2-one), 2,2,4-trimethylpentane-1,3-diol carbonate, 2,2-dimethylbutane-1,3-diol carbonate, butane-1,3-diol carbonate, 2-methylpropane-1,3-diol carbonate, pentane-2,4-diol carbonate, 2-methylbutane-1,3-diol carbonate, TMP monoallyl ether carbonate, pentaerythritol diallyl ether carbonate, 5-(2-hydroxyethyl)-1,3-dioxan-2-one, 5-[2-(benzyloxy)ethyl]-1,3-dioxan-2-one, 4-
  • cyclic carbonates having fewer than three optionally substituted methylene groups between the oxygen atoms of the carbonate group are incorporated into the polymer chain not at all or only to a small extent.
  • Cyclic anhydrides are cyclic compounds containing an anhydride group in the ring.
  • Preferred compounds are succinic anhydride, maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, diphenic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornenedioic anhydride and the chlorination products thereof, succinic anhydride, glutaric anhydride, diglycolic anhydride, 1,8-naphthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, 3- and 4-nitrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydr
  • the metering rate of the alkylene oxides or of mixtures of alkylene oxides, during the respective metering phases of the overall metered addition of alkylene oxide which lasts for ⁇ 13 h, preferably ⁇ 12 h, more preferably ⁇ 11 h, can be altered in a linear manner as a function of the mass of alkylene oxide metered in, but this alteration may also be made in a non-linear manner. It is likewise possible to control the metered addition of alkylene oxide as a function of the metering time.
  • metering profiles shown in the figures make no claim to completeness and the metering profiles are not to scale.
  • the figures serve merely to illustrate the process of the invention. They should in no way be interpreted as boundary cases that restrict the invention. More particularly, within the periods of time t 0 -t 1 , t 1 -t 2 and t 2 -t 3 , combinations of the metering profiles shown may be employed; it is likewise of course possible to combine metering profiles from the individual periods with one another, i.e., for example, a metering profile represented in dashed form from the period t 1 -t 2 with a metering profile represented in dotted form from the period t 2 -t 3 . It has been found to be advantageous to configure the transitions between the individual metering periods such that the epoxide metering profile is not altered in a discontinuous manner.
  • aging stabilizers for example antioxidants
  • the at least one H-functional starter compound is admixed with DMC catalyst and charged into a reactor; in other words, the H-functional starter compound and the DMC catalyst are charged into a reactor. It is also additionally possible to add small amounts (1 to 500 ppm) of organic or inorganic acids to the H-functional starter compound prior to the addition of the DMC catalyst, as described, for example, in WO-A 99/14258.
  • the reactor contents are first stripped with inert gas (nitrogen or a noble gas, for example argon) at temperatures of 60 to 160° C., preferably 100 to 155° C., most preferably 110 to 155° C., while stirring over a period of preferably 10 to 60 min.
  • inert gas nitrogen or a noble gas, for example argon
  • volatile constituents are removed with introduction of inert gases into the liquid phase with simultaneous application of reduced pressure, at an absolute pressure of 5 to 500 mbar.
  • the temperature can subsequently be adjusted to the reaction temperature of the downstream step, provided that it is not identical to the stripping temperature.
  • the ultimate reaction temperature can alternatively be established only in the initial phase of the alkylene oxide metering, for example with exploitation of the heat of reaction released.
  • the reaction with the at least one alkylene oxide from the time t 1 is conducted at a temperature of preferably 110° C. to 150° C., more preferably at 120-150° C.
  • the invention thus also provides a process for preparing a polyoxyalkylene polyol having a calculated equivalent molar mass of 9500 g ⁇ mol ⁇ 1 to 23 000 g ⁇ mol ⁇ 1 , preferably of 9550 g ⁇ mol ⁇ 1 to 23 000 g ⁇ mol ⁇ 1 , more preferably of 9550 g ⁇ mol ⁇ 1 to 20 000 g ⁇ mol ⁇ 1 and most preferably of 9700 to 16 000 g/mol, wherein
  • the DMC catalyst can first be activated separately by adding typically 2% to 20% by mass of alkylene oxide, based on the amount of the at least one H-functional starter compound used in step ( ⁇ ).
  • the addition of the at least one alkylene oxide can take place before, during or after the heating of the reactor contents to the stripping or reaction temperature; it preferably follows the stripping.
  • the metered addition of the amount of alkylene oxide needed for the activation of the DMC catalyst commences at time t 0 .
  • step ( ⁇ 2) After the metered addition of alkylene oxide has been stopped once typically 2% to 20% by mass of the at least one alkylene oxide, based on the at least one H-functional starter compound used in step ( ⁇ 1), have been added (step ( ⁇ 2)), the activation of the DMC catalyst is manifested by an accelerated drop in the reactor pressure, which indicates the commencement of alkylene oxide conversion. Then, i.e. on completion of activation, the remaining portion of the total amount of the at least one alkylene oxide to be fed in for preparation of the polyoxyalkylene polyol desired is fed into the reaction mixture, and the reaction with the at least one alkylene oxide from the time t 1 is conducted preferably at a temperature of 110° C. to 150° C., more preferably at 120-150° C.
  • the invention thus also provides a process for preparing a polyoxyalkylene polyol having a calculated equivalent molar mass of 9500 g ⁇ mol ⁇ 1 to 23 000 g ⁇ mol ⁇ 1 , preferably of 9550 g ⁇ mol ⁇ 1 to 23 000 g ⁇ mol ⁇ 1 , more preferably of 9550 g ⁇ mol ⁇ 1 to 20 000 g ⁇ mol ⁇ 1 and most preferably of 9700 to 16 000 g/mol, wherein
  • the reaction temperature can be varied during the polymerization (step ( ⁇ )) within the temperature limits described; for example, it may be found to be advantageous to raise the reaction temperature with increasing progress of the reaction.
  • One option is metered addition into the gas phase or directly into the liquid phase, for example via an immersed tube or a distributor ring close to the reactor base in a zone with good mixing.
  • Metered addition to the liquid phase is the preferred variant.
  • the metering units should be designed such that they self-empty, for example through provision of metering holes on the underside of the distributor ring.
  • the alkylene oxides are fed continuously to the reactor in such a way that the safety-related pressure limits of the reactor system used are not exceeded.
  • a sufficient partial inert gas pressure is maintained within the reactor during the startup and metering phase. This can be established, for example, by means of a noble gas (for example argon) or nitrogen.
  • the respective alkylene oxides can be supplied to the reactor separately or as an alkylene oxide mixture.
  • Mixing of the alkylene oxides can be achieved, for example, by means of a mixing unit present in the common metering zone (“inline blending”). It has also been found to be useful to meter alkylene oxides, on the pump pressure side, individually or in (pre)mixed form into a pumped circulation system conducted, for example, through heat exchangers. In that case, for good mixing with the reaction medium, it is advantageous to integrate a high-shear mixing unit into the alkylene oxide/reaction medium stream.
  • the temperature of the exothermic polymerization is kept at the desired level or adjusted to the desired level by cooling.
  • cooling is generally effected via the reactor wall (e.g. jacket, half-coil pipe) and by means of further heat exchange surfaces disposed internally in the reactor and/or externally in the pumped circulation system, for example in cooling coils, cooling cartridges, or plate, shell-and-tube or mixer heat exchangers.
  • These heat exchange surfaces should be designed such that effective cooling is possible even on commencement of the metering phase, i.e. with a low fill level. They should likewise be capable of effectively removing the possibly large amounts of heat of reaction in the phase of rapid metered addition of alkylene oxide, i.e. up to at least the time at which a calculated equivalent molar mass of 8000 g/mol is surpassed, with possibly high viscosity of the reacting reactor contents.
  • baffles for example flat or tubular baffles
  • cooling coils or cooling cartridges
  • the stirring power of the mixing unit may also be varied as a function of the fill level during the metering phase, in order to ensure a particularly high specific mixing power input in critical reaction phases. For example, it may be advantageous to particularly vigorously mix solids-containing dispersions which may be present at the start of the reaction, for example, in the case of use of sucrose. Moreover, particularly when solid H-functional starter compounds are used, it should be ensured through the selection of the stirrer unit that sufficient dispersion of the solids in the reaction mixture is assured.
  • stirrer geometry should contribute to reducing the foaming of reaction products.
  • the foaming of reaction mixtures can be observed, for example, after the end of the metering and post-reaction phase, when residual alkylene oxides are additionally removed under reduced pressure, at absolute pressures in the range from 1 to 500 mbar.
  • suitable stirrer units have been found to be those which achieve continuous mixing of the liquid surface.
  • the stirrer shaft has a base bearing and optionally further support bearings in the vessel. The stirrer shaft can be driven from the top or bottom (with central or eccentric arrangement of the shaft).
  • reactor bases include hemispherical, dished, flat or conical bases, for example.
  • the end of the metered addition of alkylene oxide or a change in the composition of the alkylene oxide mixture metered in may be followed by postreaction phases in which the decrease in the concentration of unreacted alkylene oxide can be quantified by monitoring the pressure. It is optionally possible to completely free the reaction mixture, after the last postreaction phase has ended, of small amounts of unconverted alkylene oxides under reduced pressure, for example at an absolute pressure of 1 to 500 mbar, or by stripping. Stripping removes volatile constituents, for example (residual) alkylene oxides, with introduction of inert gases and/or steam into the liquid phase with simultaneous application of reduced pressure (for example by passing inert gas through at an absolute pressure of 5 to 500 mbar).
  • the removal of volatile constituents is generally effected at temperatures of 20 to 200° C., preferably at 50 to 160° C., and preferably at reaction temperature with stirring.
  • Such stripping operations can also be performed in what are called stripping columns, in which an inert gas or steam stream is passed counter to the product stream. Preference is given to using stripping columns having random packings or internals for this purpose.
  • Such stripping operations can also be conducted continuously by, for example, collecting the unstripped material in a buffer vessel and feeding it continuously to the stripping column therefrom.
  • the product can be discharged from the reactor.
  • ageing stabilizers for example antioxidants
  • the polyoxyalkylene polyols prepared by the process of the invention can be reacted with organic polyisocyanates alone or optionally in a mixture with further isocyanate-reactive components, optionally in the presence of blowing agents, optionally in the presence of catalysts and optionally together with further additives, for example cell stabilizers, and as such serve as components of solid or foamed polyurethanes, for example flexible polyurethane foam, for example slabstock flexible polyurethane foam and molded flexible polyurethane foam.
  • the polyoxyalkylene polyols prepared by the process of the invention can especially also be used as components for adhesive and sealant materials. For example, they can serve as precursor polyols for the preparation of silane-terminated polyoxyalkylenes which can in turn find use in moisture-curing sealant systems.
  • the invention likewise provides polyurethanes, preferably solid or foamed polyurethanes, especially flexible polyurethane foams, for example slabstock flexible polyurethane foams and molded flexible polyurethane foams, or adhesive and sealant materials, comprising the polyoxyalkylene polyols prepared by the process of the invention.
  • polyurethanes preferably solid or foamed polyurethanes, especially flexible polyurethane foams, for example slabstock flexible polyurethane foams and molded flexible polyurethane foams, or adhesive and sealant materials, comprising the polyoxyalkylene polyols prepared by the process of the invention.
  • the OH numbers were determined by the method of DIN 53240.
  • the viscosities were determined by means of a rotary viscometer (Physica MCR 51, manufacturer: Anton Paar) by the method of DIN 53018.
  • double metal cyanide catalyst containing zinc hexacyanocobaltate, tert-butanol and polypropylene glycol having a number-average molecular weight of 1000 g/mol; described in WO-A 01/80994, example 6.
  • polypropylene glycol having a molar mass of 2000 g/mol prepared via DMC catalysis (30 ppm of DMC catalyst), obtainable from Covestro AG.
  • stirrer speeds of 320 rpm and 350 rpm set in the experiments respectively corresponded to specific power inputs of about 2.4 W/L and about 3 W/L (gate stirrer) based on the reactor volume.
  • a 10 L laboratory autoclave was charged with 609.8 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.420 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5390.6 g of propylene oxide were metered into the headspace of the autoclave within 12.08 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • the propylene oxide (PO) was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 609.7 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.424 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5390.6 g of propylene oxide were metered into the headspace of the autoclave within 12.08 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • the PO was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 609.6 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.427 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5390.6 g of propylene oxide were metered into the headspace of the autoclave within 10.68 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • the PO was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 609.5 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.426 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5390.7 g of propylene oxide were metered into the headspace of the autoclave within 17.85 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • the PO was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 609.5 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.422 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5390.7 g of propylene oxide were metered into the headspace of the autoclave within 13.31 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • the PO was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 609.5 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.426 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5390.8 g of propylene oxide were metered into the headspace of the autoclave within 11.07 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • the PO was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 471.9 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.483 g of DMC catalyst, the contents of the autoclave were stripped at 130° C. while stirring (gate stirrer) at 350 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. By means of this distributor ring, a total of 5528.6 g of propylene oxide were then metered in, likewise initially at 130° C.
  • a 10 L laboratory autoclave was charged with 471.5 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.479 g of DMC catalyst, the contents of the autoclave were stripped at 130° C. while stirring (gate stirrer) at 350 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. By means of this distributor ring, a total of 5528.7 g of propylene oxide were then metered in, at first likewise at 130° C. with stirring at 350 rpm, at a stirrer speed of 350 rpm. This gave a total metering time for the propylene oxide of 18.3 h.
  • the PO was fed into the autoclave using the following metering profile:
  • a 10 L laboratory autoclave was charged with 471.4 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.485 g of DMC catalyst, the contents of the autoclave were stripped at 130° C. while stirring (gate stirrer) at 350 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. By means of this distributor ring, a total of 5528.7 g of propylene oxide were then metered in, at first likewise at 130° C. with stirring at 350 rpm, at a stirrer speed of 350 rpm. This gave a total metering time for the propylene oxide of 12.8 h.
  • the PO was fed into the autoclave using the following metering profile:
  • a 10 L laboratory autoclave was charged with 471.5 g of ACCLAIM® Polyol 2200N under a nitrogen atmosphere. After addition of 0.485 g of DMC catalyst, the contents of the autoclave were stripped at 130° C. while stirring (gate stirrer) at 350 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. By means of this distributor ring, a total of 5528.8 g of propylene oxide were then metered in, at first likewise at 130° C. with stirring at 350 rpm, at a stirrer speed of 350 rpm. This gave a total metering time for the propylene oxide of 12.9 h.
  • the PO was fed into the autoclave using the following metering profile:
  • a 10 L laboratory autoclave was charged with 609.5 g of ACCLAIM® Polyol 2200 N under a nitrogen atmosphere. After addition of 0.422 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5289.5 g of a mixture of 91.7% by mass of PO and 8.3% by mass of ethylene oxide (EO) were metered into the headspace of the autoclave within 10.73 hours. The calculated equivalent molar mass was 9696 g/mol and the calculated target OHN (OHN target ) was 5.79 mg KOH/g.
  • composition of the alkylene oxide mixture was kept constant at 91.7% by mass of PO and 8.3% by mass of EO over all the metering phases. It was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 609.5 g of ACCLAIM® Polyol 2200 N under a nitrogen atmosphere. After addition of 0.424 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5390.1 g of a mixture of 70.0% by mass of PO and 30.0% by mass of EO were metered into the headspace of the autoclave within 10.73 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • composition of the alkylene oxide mixture was kept constant at 70.0% by mass of PO and 30.0% by mass of EO over all the metering phases. It was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 609.6 g of ACCLAIM® Polyol 2200 N under a nitrogen atmosphere. After addition of 0.423 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5389.6 g of a mixture of 90.0% by mass of PO and 10.0% by mass of EO were metered into the headspace of the autoclave within 11.08 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • composition of the alkylene oxide mixture was kept constant at 90.0% by mass of PO and 10.0% by mass of EO over all the metering phases. It was fed into the autoclave using the following metering and temperature profile:
  • a 10 L laboratory autoclave was charged with 609.5 g of ACCLAIM® Polyol 2200 N under a nitrogen atmosphere. After addition of 0.425 g of DMC catalyst, the contents of the autoclave were stripped at 123° C. while stirring (gate stirrer) at 320 rpm under reduced pressure at an absolute pressure of 100 to 120 mbar with introduction of 50 mL of nitrogen per minute via a distributor ring beneath the liquid level for 30 min. Then, likewise initially at 123° C. and with stirring at 320 rpm, a total of 5390.2 g of a mixture of 70.0% by mass of PO and 30.0% by mass of EO were metered into the headspace of the autoclave within 10.66 hours. The calculated equivalent molar mass was 9859 g/mol and the calculated target OHN (OHN target ) was 5.69 mg KOH/g.
  • composition of the alkylene oxide mixture was kept constant at 70.0% by mass of PO and 30.0% by mass of EO over all the metering phases. It was fed into the autoclave using the following metering and temperature profile:

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